Thermoelectric materials synthesized by self-propagating high temperature synthesis process and methods thereof

ABSTRACT

The disclosure relates to thermoelectric materials prepared by self-propagating high temperature synthesis (SHS) process combining with Plasma activated sintering and methods for preparing thereof. More specifically, the present disclosure relates to the new criterion for combustion synthesis and the method for preparing the thermoelectric materials which meet the new criterion.

FIELD

The present disclosure relates to thermoelectric materials prepared byself-propagating high temperature synthesis (SHS) process combining withplasma activated sintering (PAS) and a method for preparing the same.More specifically, the present disclosure relates to a new criterion forcombustion synthesis and the method for preparing thermoelectricmaterials which can meet the new criterion.

BACKGROUND

In the heat flow of the energy consumption in the world, there is about70% of the total energy wasted in the form of heat. If those largequantities of waste heat can be recycled effectively, it would reliefthe energy crisis in the world. Thermoelectric (TE) materials convertheat into electricity directly through the Seebeck effect.Thermoelectric materials offer many advantages including: no movingparts; small and lightweight; maintenance-free; no pollution;acoustically silent and electrically “quiet”. Thermoelectric energyconversion has drawn a great attention for applications in areas such assolar thermal conversion, industrial waste heat recovery. The efficiencyof a TE material is strongly related to its dimensionless figure ofmerit ZT, defined as ZT=α²σT/κ, where α, σ; κ and T are the Seebeckcoefficient, electrical conductivity, total thermal conductivity, andthe absolute temperature, respectively. To achieve high efficiency, alarge ZT is required. High electrical conductivity, large Seebeckcoefficient, and low thermal conductivity are necessary for a highefficient TE material. However those three parameters relate with eachother. Hence decoupling the connection of those parameters is key issueto improve the thermoelectric performance A lot of investigation showsthat nanostructure engineering can weak the coupling to enhance thethermoelectric property.

Until now, most researchers have utilized top down approach to obtainnanostructure (mechanic alloy, melt spinning, etc). But all thoseprocessing is of high energy consumption. In addition, some investigatorused bottom up fabrication to synthesize low dimensional material (Wetchemical method). Efficient synthesis and its adaptability to alarge-scale industrial processing are important issues determining theeconomical viability of the fabrication process. So far, thermoelectricmaterials have been synthesized mostly by one of the following methods:melting followed by slow cooling; melting followed by long timeannealing, multi-step solid state reactions, and mechanical alloying.Each such processing is time and energy consuming and not always easilyscalable. Moreover, it is often very difficult to control the desiredstoichiometry and microstructure. All those difficulty is ofuniversality in all those thermoelectric material. Hence developing atechnology which not only can synthesize the samples in large scale andshort period but also can control the composition and microstructureprecisely is of vital importance for the large scale application.

Self-propagating high-temperature synthesis (SHS) is a method forsynthesizing compounds by exothermic reactions. The SHS method, oftenreferred to also as the combustion synthesis, relies on the ability ofhighly exothermic reactions to be self-sustaining, i.e., once thereaction is initiated at one point of a mixture of reactants, itpropagates through the rest of the mixture like a wave, leaving behindthe reacted product. What drives this combustion wave is exothermic heatgenerated by an adjacent layer. In contrast with some other traditionalmethod, the synthesis process is energy saving, exceptionally rapid andindustrially scalable. Moreover, this method does not rely on anyequipment. Base on the experiments, Merzhanov suggested an empiricalcriterion, T_(ad)>1800 K, as the necessary precondition forself-sustainability of the combustion wave, where T_(ad) is the maximumtemperature to which the reacting compact is raised as the combustionwave passes through. It restricts the scope of materials that can besuccessfully synthesized by SHS processing.

SUMMARY

In order to solve the problem of existing technology, the objects of thepresent disclosure is to provide an ultra-fast fabrication method forpreparing high performance thermoelectric materials. By using thismethod, it can control the composition very precisely, shorts thesynthesis period, and is easy to scale up to kilogram. Highthermoelectric performance can be obtained. Moreover, we found that thecriterion often quoted in the literature as the necessary preconditionfor self-sustainability of the combustion wave, T_(ad)≥1800 K, whereT_(ad) is the maximum temperature to which the reacting compact israised as the combustion wave passes through, is not universal andcertainly not applicable to thermoelectric compound semiconductors.Instead, we offer new empirically-based criterion, T_(ad)/T_(mL)>1,i.e., the adiabatic temperature must be high enough to melt the lowermelting point component. This new criterion covers all materialssynthesized by SHS, including the high temperature refractory compoundsfor which the T_(ad)≥1800 K criterion was originally developed. Our workopens a new avenue for ultra-fast, low cost, mass production fabricationof efficient thermoelectric materials and the new insight into thecombustion process greatly broadens the scope of materials that can besuccessfully synthesized by SHS processing.

In accordance with the present disclosure, the above objects of thepresent disclosure can be achieved by the following steps.

1. The new criterion for the combustion synthesis of binary compounds isas following.

1) The adiabatic temperatures T_(ad) of the binary compounds arecalculated by thermodynamic data (enthalpy of formation and the molarspecific heat of the product) and Eq. (1). Where Δ_(f)H_(298K) isenthalpy of formation for the binary compounds, T is temperature,H_(298K) ⁰ is the enthalpy of the binary compounds at 298 K, and C isthe molar specific heat of the product and the integral includes latentheats of melting, vaporization, and phase transitions, if any present.The reactants for the combustion reaction are pure elemental for thebinary compounds.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) CdT  (1)

When there is no phase transition and the adiabatic temperature is lowerthan the melting point of the binary compound, Equation (1) can besimplified into Equation (2) shown below, where C_(p) is the the molarspecific heat of the product in solid state.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT  (2)

When there is no phase transition and the adiabatic temperature ishigher than the melting point of the binary compound and lower than theboiling point of of the binary compound, Equation (1) can be simplifiedinto Equation (3) shown below, where C_(p), C″_(p) is the the molarspecific heat of the product in solid state and liquid staterespectively, T_(m) is the melting point of the binary compound, ΔH_(m)is the enthalpy change during fusion processing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(m) C _(p) dT+ΔH_(m)+∫_(T) _(m) ^(T) ^(ad) C″ _(p) dT  (3)

When there is no phase transition and the adiabatic temperature ishigher than the boiling point of of the binary compound, Equation (1)can be simplified into Equation (4) shown below, where C_(p), C″_(p),C′″_(p) is the the molar specific heat of the product in solid, liquidand gaseous state respectively, T_(m), T_(b) is the melting point andboiling point of the binary compound, respectively. ΔH_(m), ΔH_(b) isthe enthalpy change during fusion and gasification processingrespectively.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(m) C _(p) dT+ΔH_(m)+∫_(Tm) ^(T) ^(B) C″ _(p) dT+ΔH _(B)+∫_(TB) ^(T) ^(ad) C″ _(p)dT  (4)

When phase transition exists during the heating processing and theadiabatic temperature is higher than the phase transition temperature ofthe binary compound, the Equation (1) can be simplified into Equation(5) as below, where C_(p), C′_(p) is the the molar specific heat of theproduct in solid before or after phase transition respectively, T_(tr)is the phase transition temperature of the binary compound, ΔH_(tr) isthe enthalpy change during phase transition processing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(ad) C′ _(p) dT+ΔH _(m)+∫_(T) _(tr) ^(T) ^(ad)C′ _(p) dT  (5)

When phase transition exists during the heating processing and theadiabatic temperature is higher than the phase transition temperatureand the melting point of the binary compound, the Equation (1) can besimplified into Equation (6) as below, where C_(p), C′_(p), C″_(p) isthe molar specific heat of the product in solid before or after phasetransition and the molar specific heat of the product in liquid staterespectively, T_(tr), T_(m) is the phase transition temperature andmelting point of the binary compound respectively, ΔH_(tr), ΔH_(m) isthe enthalpy change during phase transition processing and fusionprocessing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(m) C′ _(p) dT+ΔH _(m)+∫_(T) _(m) ^(T) ^(ad) C″_(p) dT  (6)

When phase transition exists during the heating processing and theadiabatic temperature is higher than the phase transition temperatureand the boiling point of the binary compound, the Equation (1) can besimplified into Equation (7) as below, where C_(p), C′_(p), C″_(p) isthe molar specific heat of the product in solid before or after phasetransition and the molar specific heat of the product in liquid staterespectively, T_(tr), T_(m) is the phase transition temperature andmelting point of the binary compound respectively, ΔH_(tr), ΔH_(m) isthe enthalpy change during phase transition processing and fusionprocessing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(m) C′ _(p) dT+ΔH _(m)+∫_(T) _(m) ^(T) ^(B) C″_(p) dT+ΔH _(B)+∫_(T) _(b) ^(T) ^(ad) C′″ _(p) dT  (7)

2. T_(mL) represents the melting point of the component with lowermelting point. The SHS reaction to be self-sustaining, the value ofT_(ad)/T_(m,L) should be more than 1, i.e., the heat released in thereaction must be high enough to melt the component with the lowermelting point, or the combustion wave can not be self propagated.

3. Based on the new criterion for combustion synthesis of thermoelectriccompounds, the above and other objects can be accomplished by theprovision of a method for preparing thermoelectric materials by SHScombining Plasma activated sintering which comprises following steps:

-   1) Choose two single elemental as the starting material for the    reaction-   2) The adiabatic temperatures T_(ad) of the binary compounds are    calculated by thermodynamic data (enthalpy of formation and the    molar specific heat of the product) and Eq. (1). Where Δ_(f)H_(298K)    is enthalpy of formation for the binary compounds, T is temperature,    H_(298K) ⁰ is the enthalpy of the binary compounds at 298 K, and C    is the molar specific heat of the product and the integral includes    latent heats of melting, vaporization, and phase transitions, if any    present. The reactants for the combustion reaction are pure    elemental for the binary compounds.    −Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) CdT  (1)

When there is no phase transition and the adiabatic temperature is lowerthan the melting point of the binary compound, the Equation (1) can besimplified into Equation (2) as below, where C_(p) is the the molarspecific heat of the product in solid state.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT  (2)

When there is no phase transition and the adiabatic temperature ishigher than the melting point of the binary compound and lower than theboiling point of of the binary compound, the Equation (1) can besimplified into Equation (3) as below, where C_(p), C″_(p) is the themolar specific heat of the product in solid state and liquid staterespectively, T_(m) is the melting point of the binary compound, ΔH_(m)is the enthalpy change during fusion processing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(m) C _(p) dT+ΔH_(m)+∫_(T) _(m) ^(T) ^(ad) C″ _(p) dT  (3)

When there is no phase transition and the adiabatic temperature ishigher than the boiling point of of the binary compound, the Equation(1) can be simplified into Equation (4) as below, where C_(p), C″_(p),C′″_(p) is the the molar specific heat of the product in solid, liquidand gaseous state respectively, T_(m), T_(b) is the melting point andboiling point of the binary compound, respectively. ΔH_(m), ΔH_(b) isthe enthalpy change during fusion and gasification processingrespectively.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(m) C _(p) dT+ΔH_(m)+∫_(T) _(m) ^(T) ^(B) C″ _(p) dT+ΔH _(B)+∫_(T) _(B) ^(T) ^(ad) C′″_(p) dT  (4)

When phase transition exists during the heating processing and theadiabatic temperature is higher than the phase transition temperature ofthe binary compound, the Equation (1) can be simplified into Equation(5) as below, where C_(p), C′_(p) is the the molar specific heat of theproduct in solid before or after phase transition respectively, T_(tr)is the phase transition temperature of the binary compound, ΔH_(tr) isthe enthalpy change during phase transition processing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(ad) C′ _(p) dT  (5)

When phase transition exists during the heating processing and theadiabatic temperature is higher than the phase transition temperatureand the melting point of the binary compound, the Equation (1) can besimplified into Equation (6) as below, where C_(p), C′_(p), C″_(p) isthe molar specific heat of the product in solid before or after phasetransition and the molar specific heat of the product in liquid staterespectively, T_(tr), T_(m) is the phase transition temperature andmelting point of the binary compound respectively, ΔH_(tr), ΔH_(m) isthe enthalpy change during phase transition processing and fusionprocessing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(m) C′ _(p) dT+ΔH _(m)+∫_(T) _(m) ^(T) ^(ad) C″_(p) dT  (6)

When phase transition exists during the heating processing and theadiabatic temperature is higher than the phase transition temperatureand the boiling point of the binary compound, the Equation (1) can besimplified into Equation (7) as below, where C_(p), C′_(p), C″_(p) isthe molar specific heat of the product in solid before or after phasetransition and the molar specific heat of the product in liquid staterespectively, T_(tr), T_(m) is the phase transition temperature andmelting point of the binary compound respectively, ΔH_(tr), ΔH_(m) isthe enthalpy change during phase transition processing and fusionprocessing.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(m) C′ _(p) dT+ΔH _(m)+∫_(T) _(m) ^(T) ^(B) C″_(p) dT+ΔH _(B)+∫_(T) _(b) ^(T) ^(ad) C′″ _(p) dT  (7)

-   3) T_(mL) represents the melting point of the component with lower    melting point. The SHS reaction to be self-sustaining, the value of    T_(ad)/T_(m,L) should be more than 1, i.e., the heat released in the    reaction must be high enough to melt the component with the lower    melting point, or the combustion wave can not be self propagated.-   4) Self propagating high temperature synthesis: Stoichiometric    amounts of single elemental powders with high purity were weighed    and mixed in the agate mortar and then cold-pressed into a pellet.    The pellet obtained was initiated by point-heating a small part    (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. Single phase binary compounds are obtained after SHS.

According to the above step, the binary compounds are mostlythermoelectric material, high temperature ceramics and intermetallic.

According to the above step, the purity of the single elemental powderis better than 99.99%.

According to the above step, the pellet was sealed in a silica tubeunder the pressure of 10⁻³ Pa or Ar atmosphere. The components reactunder the pressure of 10⁻³ Pa or Ar atmosphere.

According to the above step, the pellet after SHS was crushed intopowders and then sintered by spark plasma sintering to obtain the bulks.

Moreover, we found that the criterion suggested by Merzhanov as thenecessary precondition for self-sustainability of the combustion wave,T_(ad)≥1800 K, where T_(ad) is the maximum temperature to which thereacting compact is raised as the combustion wave passes through, is notuniversal and certainly not applicable to thermoelectric compoundsemiconductors. Instead, we offer new empirically-based criterion,T_(ad)/T_(mL)>1, i.e., the adiabatic temperature must be high enough tomelt the lower melting point component. When this happens, the highermelting point component rapidly dissolves in the liquid phase of thefirst component and generates heat at a rate high enough to sustainpropagation of the combustion wave. This new criterion covers allmaterials synthesized by SHS, including the high temperature refractorycompounds for which the T_(ad)≥1800 K criterion was originallydeveloped. Our work opens a new avenue for ultra-fast, low cost, massproduction fabrication of efficient thermoelectric materials and the newinsight into the combustion process greatly broadens the scope ofmaterials that can be successfully synthesized by SHS processing.

It is another object for present disclosure to provide a method forpreparing ternary or quarternary thermoelectric materials. Chooseelemental powder with high purity as the starting material for thereaction. Stoichiometric amounts of single elemental powders with highpurity were weighed and mixed in the agate mortar and then cold-pressedinto a pellet. The pellet obtained was initiated by point-heating asmall part (usually the bottom) of the sample. Once started, a wave ofexothermic reactions (combustion wave) passes through the remainingmaterial as the liberated heat of fusion in one section is sufficient tomaintain the reaction in the neighboring section of the compact. Andthen the pellet was cool down to room temperature in the air. Singlephase compounds are obtained after SHS. The pellet was crushed intopowder and then sintered by spark plasma sintering to obtain the bulkthermoelectric materials. The detailed synthesis procedure for ternaryor quarternary thermoelectric materials is as following.

The ultra-fast synthesis method for preparing high performanceHalf-Heusler thermoelectric materials with low cost comprises the stepsof

-   1) Stoichiometric amounts ABX of high purity single elemental A, B,    X powders were weighed and mixed in the agate mortar and then    cold-pressed into a pellet.-   2) The pellet was sealed in a silica tube under the pressure of 10⁻³    Pa and was initiated by point-heating a small part (usually the    bottom) of the sample. Once started, a wave of exothermic reactions    (combustion wave) passes through the remaining material as the    liberated heat of fusion in one section is sufficient to maintain    the reaction in the neighboring section of the compact. And then the    pellet was cool down to room temperature in the air or quenched in    the salt water.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then sintered by PAS. The densely bulks half    heusler with excellent thermoelectric properties is obtained after    PAS.

In step 1), what we choose for elemental A can be the elemental in IIIB,IVB, and VB column of periodic Table, Such as one of or the mixture ofthe Ti, Zr, Hf, Sc, Y, La, V, Nb, Ta. What we choose for elemental B canbe the elemental in VIIIB column of periodic Table, such as one of orthe mixture of the Fe, Co, Ni, Ru, Rh, Pd, and Pt. What we choose forelemental B can be the elemental in IIIA, IVA, VA column of periodicTable, such as one of or the mixture of the Sn, Sb, and Bi. In step 3),the parameter for spark plasma sintering is with the temperature above850° C. and the pressure around 30-50 MPa.

The detail of the ultra-fast preparation method of high performanceBiCuSeO based thermoelectric material is as following.

-   1) Weigh Bi₂O₃, PbO, Bi, Cu, and Se according to the stoichiometric    ratio (1−p):3p:(1−p):3:3(p=0, 0.02, 0.04, 0.06, 0.08, 0.1) and mix    them in the agate mortar and then cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water.-   3) The obtained pellet Bi_(1−p)Pb_(p)CuSe in step 2) was crushed,    hand ground into a fine powder, and then sintered by PAS. The    densely bulks Bi_(1−p)Pb_(p)CuSe with excellent thermoelectric    properties is obtained after PAS.

In step 3), the parameter for spark plasma sintering is with thetemperature above 670° C. and the pressure of 30 MPa holding for 5-7min.

The detail of the ultra-fast preparation method of high performanceBi₂Te₃ based thermoelectric material is as following.

-   1) Stoichiometric amounts Bi₂Te_(3−x)Se_(x) of high purity single    elemental Bi, Te, Se powders were weighed and mixed in the agate    mortar and then cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water.-   3) The obtained pellet Bi₂Te_(3−x)Se_(x) in step 2) was crushed,    hand ground into a fine powder, and then sintered by PAS. The    densely bulks Bi₂Te_(3−x)Se_(x) with excellent thermoelectric    properties is obtained after PAS.

In step 3), load the Bi₂Te_(3−x)Se_(x) powder with single phase into thegraph die. the parameter for spark plasma sintering is with thetemperature around 420-480° C. and the pressure of 20 MPa holding for 5min.

The detail of the ultra-fast preparation method of high performancePbS_(1−x)Se_(x) thermoelectric material is as following.

-   1) Stoichiometric amounts PbS_(1−x)Se_(x) of high purity single    elemental Pb, S, Se powders were weighed and mixed in the agate    mortar and then cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water.-   3) The obtained pellet PbS_(1−x)Se_(x) in step 2) was crushed, hand    ground into a fine powder, and then sintered by PAS. The densely    bulks PbS_(1−x)Se_(x) with excellent thermoelectric properties is    obtained after PAS.

In step 3), load the PbS_(1−x)Se_(x) powder with single phase into thegraphite die. The parameter for spark plasma sintering is with thetemperature of 550° C. and the pressure of 35 MPa holding for 7 min.

The detail of the ultra-fast preparation method of high performanceMg₂Si based thermoelectric material is as following.

-   1) Stoichiometric amounts Mg₂₍₁₊₀₀₂₎Si_(1−n)Sb_(n)(0≤n≤0.025) of    high purity single elemental Mg, Si, Sb powders were weighed and    mixed in the agate mortar and then cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water.-   3) The obtained pellet Mg₂₍₁₊₀₀₂₎Si_(1−n)Sb_(n)(0≤n≤0.025) in    step 2) was crushed, hand ground into a fine powder, and then    sintered by PAS. The densely bulks PbS_(1−x)Se_(x) with excellent    thermoelectric properties is obtained after PAS.

In step 3), load the Mg₂₍₁₊₀₀₂₎Si_(1−n)Sb_(n)(0≤n≤0.025) powder withsingle phase into the graphite die. The parameter for spark plasmasintering is with the temperature of 800° C. with the heating rate 100°C./min and the pressure of 33 MPa holding for 7 min. Since the contentof Sb in Mg₂₍₁₊₀₀₂₎Si_(1−n)Sb_(n)(0≤n≤0.025) is very low, the impact ofSb on the SHS processing can be ignored.

The detail of the ultra-fast preparation method of high performanceCu_(a)MSn_(b)Se₄ thermoelectric material is as following.

-   1) Stoichiometric amounts Cu_(a)MSn_(b)Se₄ (M=Sb, Zn, or Cd; a=2 or    3; b=1 or 0) of high purity single elemental Cu, M, Sn, Se powders    were weighed and mixed in the agate mortar and then cold-pressed    into a pellet. For Cu₃SbSe₄, Weigh the elemental Cu, Sb Se powder    according to the ratio of Cu:Sb:Se=3:(1.01˜1.02):4, and mixed in the    agate mortar and then cold-pressed into a pellet. For Cu₂ZnSnSe₄,    Weigh the elemental Cu, Zn, Sn, Se powder according to the ratio of    Cu:Zn:Sn:Se=2:1:1:4, and mixed in the agate mortar and then    cold-pressed into a pellet. For Cu₂CdSnSe₄, Weigh the elemental Cu,    Cd, Sn, Se powder according to the ratio of Cu:Cd:SN:Se=2:1:1:4, and    mixed in the agate mortar and then cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 1⁰⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water. The obtained pellet    Cu_(a)MSn_(b)Se₄ in step 2) was crushed, hand ground into a fine    powder.

The detail of the ultra-fast preparation method of high performanceCu₂SnSe₃ thermoelectric material is as following.

-   1) Weigh high purity single elemental Cu, Sn, Se powders according    to the ratio of Cu:Se:Sn=2.02:3.03:1 and mixed in the agate mortar    and then cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water.-   3) The obtained pellet Cu₂SnSe₃ in step 2) was crushed, hand ground    into a fine powder, and then sintered by PAS. The densely bulks    Cu₂SnSe₃ with excellent thermoelectric properties is obtained after    PAS.

In step 3), load the Cu₂SnSe₃ powder with single phase into the graphitedie. The parameter for spark plasma sintering is with the temperaturearound 500-550° C. with the heating rate 50-100° C./min and the pressurearound 30-35 MPa holding for 5-7 min.

The detail of the ultra-fast preparation method of high performanceCoSb₃ based thermoelectric material is as following.

-   1) Stoichiometric amounts Co_(4−e)M_(e)Sb_(12−f)Te_(f) (0≤e≤1.0,    0≤f≤1.0, M═Fe or Ni) of high purity single elemental Co, M, Sb, Te    powders were weighed and mixed in the agate mortar and then    cold-pressed into a pellet.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by point-heating a small    part (usually the bottom) of the sample. Once started, a wave of    exothermic reactions (combustion wave) passes through the remaining    material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air or quenched in the salt water.-   3) The obtained pellet Co_(4−e)M_(e)Sb_(12−f)Te_(f) (0≤e≤1.0,    0≤f≤1.0, M═Fe or Ni) in step 2) was crushed, hand ground into a fine    powder, and then sintered by PAS. The densely bulks    Co_(4−e)M_(e)Sb_(12−f)Te_(f) (0≤e≤1.0, 0≤f≤1.0, M═Fe or Ni) with    excellent thermoelectric properties is obtained after PAS.

In step 3), load the Co_(4−e)M_(e)Sb_(12−f)Te_(f) (0≤e≤1.0, 0≤f≤1.0,M═Fe or Ni) powder with single phase into the graphite die. Theparameter for spark plasma sintering is with the temperature of 650° C.with the heating rate 100° C./min and the pressure of 40 MPa holding for8 min.

Compared with the conventional synthesis technique, the advantage of thedisclosure is as below.

-   -   1. SHS method is very convenient and does not rely on any        equipment. But for some other methods such as Mechanic alloy,        Melt spinning, etc all those processing demand complicated        equipments. For chemical method, the yield is very low and it is        very difficult to condense the sample. Moreover all those        processing except SHS processing is energy consuming        Self-propagating high-temperature synthesis (SHS) is a method        for synthesizing compounds by exothermic reactions. The SHS        method, often referred to also as the combustion synthesis,        relies on the ability of highly exothermic reactions to be        self-sustaining, i.e., once the reaction is initiated at one        point of a mixture of reactants, it propagates through the rest        of the mixture like a wave, leaving behind the reacted product.        What drives this combustion wave is exothermic heat generated by        an adjacent layer. In contrast with some other traditional        method, the synthesis process is energy saving, exceptionally        rapid and industrially scalable.    -   2. Since Self-propagating high-temperature synthesis (SHS) can        be finished in a very short time. It can control the composition        very precisely. Moreover, the Non-equibrium microstructure can        be obtained since large temperature gradient exists during the        SHS processing.    -   3. It shortens the synthesis periods very significantly by about        90% in comparison with conventional method.

Based on the above content, without departing from the basic technicalconcept of the present disclosure, under the premise of ordinary skillin the art based on the knowledge and means of its contents can alsohave various forms of modification, substitution or changes, such asT_(ad)>T_(mL), or T_(mL)<T_(ad).

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows Powder XRD pattern of compounds thermoelectric after SHSfor embodiment example 1.

FIG. 2 shows Powder XRD pattern of Sb₂Te₃ and MnSi_(1.70) pellets afterSHS in different region for embodiment example 2.

FIG. 3 shows the ratio of between T_(ad) and T_(mL) for compoundsthermoelectrics PbS, PbSe, Mg₂Si, Mg₂Sn, Cu₂Se, Bi₂Se₃, PbTe, Bi₂Te₃ inembodiment example 1 and high temperature intermetallic and refractoryin embodiment example 3.

FIG. 4 shows XRD pattern of Cu₂Se after SHS (in step 2) and afterSHS-PAS (in step 3) of embodiment example 4

FIG. 5 shows FESEM image of Cu₂Se after SHS (in step 2) of embodimentexample 4

FIG. 6 shows FESEM image of Cu₂Se after SHS-PAS (in step 3) ofembodiment example 4

FIG. 7 shows the temperature dependence of ZT (in step 3) of embodimentexample 4.

FIG. 8 shows XRD pattern of the powder in step 2 of embodiment example5.1 and bulk in step 3 of embodiment example 5.1

FIG. 9 shows the microstructure of the powder in step 2 of embodimentexample 5.1.

FIG. 10 shows XRD pattern of the powder in step 2 of embodiment example5.2

FIG. 11 shows the XRD pattern of the powder in step 2 of embodimentexample 5.3 and bulk in step 3 of embodiment example 5.3

FIG. 12 shows the temperature dependence of power factor and ZT of bulksobtained in step 3 of embodiment example 5.3

FIG. 13 shows the XRD pattern of the powder obtained in step 2 ofembodiment example 6

FIG. 14 shows the XRD pattern of the Bi₂Te_(2.7)Se_(0.3) compound instep 2 of embodiment example 7.1 and Bi₂Te_(2.7)Se_(0.3) bulk in step 3of embodiment example 7.1

FIG. 15(a) shows FESEM image of Bi₂Te_(2.7)Se_(0.3) after SHS-PAS (instep 3) of embodiment example 7.1. FIG. 15(b) shows enlarged FESEM imageof Bi₂Te_(2.7)Se_(0.3) after SHS-PAS.

FIG. 16 shows temperature dependence of ZT for Bi₂Te_(2.7)Se_(0.3)compound (in step 3) of embodiment example 7.1 and the data from thereference.

FIG. 17 shows the XRD pattern of the Bi₂Te_(2.7)Se_(0.3) compound instep 2 of embodiment example 7.2

FIG. 18 shows the XRD pattern of the Bi₂Te₂Se compound in step 2 ofembodiment example 7.3

FIG. 19 shows the XRD pattern of powder after SHS in embodiment example8.1

FIG. 20 shows the XRD pattern of powder after SHS and after SHS-PAS ofembodiment example 8.2

FIG. 21 shows the XRD pattern of powder after SHS in embodiment example8.3

FIG. 22 shows the XRD pattern of powder after SHS in embodiment example8.4

FIG. 23(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 8.5. FIG. 23(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 8000) in embodiment example8.4. FIG. 23(c) shows the temperature dependence of ZT in comparisonwith the sample synthesized by melting method in embodiment example 8.4.

FIG. 24(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 9.1. FIG. 24(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 10000) in embodiment example9.1. FIG. 24(c) shows SEM image of the bulks after SHS-PAS (with themagnification 2000 and 10000) in embodiment example 9.1.

FIG. 25(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 9.2. FIG. 25(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 10000) in embodiment example9.2. FIG. 25(c) shows SEM image of the bulks after SHS-PAS (with themagnification 2000 and 10000) in embodiment example 9.2.

FIG. 26(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 9.3. FIG. 26(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 10000) in embodiment example9.3. FIG. 26(c) shows SEM image of the bulks after SHS-PAS (with themagnification 2000 and 10000) in embodiment example 9.3.

FIG. 27(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 9.4. FIG. 27(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 10000) in embodiment example9.4. FIG. 27(c) shows SEM image of the bulks after SHS-PAS (with themagnification 2000 and 10000) in embodiment example 9.4.

FIG. 28(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 9.5. FIG. 28(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 10000) in embodiment example9.5. FIG. 28(c) shows SEM image of the bulks after SHS-PAS (with themagnification 2000 and 10000) in embodiment example 9.5. FIG. 28(d)shows the temperature dependence of ZT in comparison with the samplesynthesized by other method in embodiment example 9.5.

FIG. 29 shows the XRD pattern of Cu₃SbSe₄ powder after SHS in step 3 ofembodiment example 10.1.

FIG. 30 shows the XRD pattern of Cu₃SbSe₄ powder after SHS in step 3 ofembodiment example 10.2.

FIG. 31 shows the XRD pattern of Cu₂ZnSnSe₄ powder after SHS in step 3of embodiment example 10.3.

FIG. 32 shows the XRD pattern of Cu₂ZnSnSe₄ powder after SHS in step 3of embodiment example 10.4.

FIG. 33 shows the XRD pattern of Cu₂CdSnSe₄ powder after SHS in step 3of embodiment example 10.5.

FIG. 34 shows the XRD pattern of Cu₃SbSe₄ powder after SHS in step 3 ofembodiment example 10.6.

FIG. 35 shows the XRD pattern of Cu₂SnSe₃ powder after SHS in step 2 ofembodiment example 11.1

FIG. 36 shows the XRD pattern of Cu₂SnSe₃ powder after SHS in step 2 ofembodiment example 11.2

FIG. 37 shows the XRD pattern of Cu₂SnSe₃ powder after SHS-PAS ofembodiment example 11.2

FIG. 38 shows the temperature dependence of ZT for Cu₂SnSe₃ inembodiment example 11.2

FIG. 39 shows the XRD pattern of Cu₂SnSe₃ powder after SHS in embodimentexample 11.3

FIG. 40(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 12.1. FIG. 40(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 20000) in step 2 ofembodiment example 12.1. FIG. 40(c) shows SEM image of the bulks afterSHS-PAS (with the magnification 5000 and 20000) in step 3 of embodimentexample 12.1.

FIG. 41(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 12.2. FIG. 41(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 20000) in step 2 ofembodiment example 12.2. FIG. 41(c) shows SEM image of the bulks afterSHS-PAS (with the magnification 5000 and 20000) in step 3 of embodimentexample 12.2.

FIG. 42(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 12.3. FIG. 42(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 20000) in step 2 ofembodiment example 12.3. FIG. 42(c) shows SEM image of the bulks afterSHS-PAS (with the magnification 5000 and 20000) in step 3 of embodimentexample 12.3.

FIG. 43(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 12.4. FIG. 43(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 20000) in step 2 ofembodiment example 12.4. FIG. 43(c) shows SEM image of the bulks afterSHS-PAS (with the magnification 5000 and 20000) in step 3 of embodimentexample 12.4.

FIG. 44(a) shows the XRD pattern of powder after SHS and after SHS-PASof embodiment example 12.5. FIG. 44(b) shows SEM image of the powderafter SHS (with the magnification 5000 and 20000) in step 2 ofembodiment example 12.5. FIG. 44(c) shows SEM image of the bulks afterSHS-PAS (with the magnification 5000 and 20000) in step 3 of embodimentexample 12.5.

FIG. 45(a) shows the temperature dependence of ZT forCo_(3.5)Ni_(0.5)Sb₁₂ in step 3 of embodiment example 12.1 compared withthe data from reference. (in the reference, the sample synthesized byMelt-annealing and PAS. It takes about 240 h)

FIG. 45(b) shows the temperature dependence of ZT forCo₄Sb_(11.4)Te_(0.6) in step 3 of embodiment example 12.5 compared withthe data from reference. (In the reference, the sample is synthesized byMelt-annealing and PAS. It takes about 168 h)

DETAILED DESCRIPTION

For a better understanding of the present disclosure, severalembodiments are given to further illustrate the disclosure, but thepresent disclosure is not limited to the following embodiments

Embodiment Example 1 Embodiment Example 1.1

Based on the new criterion, the detailed synthesis procedure of Bi₂Te₃is as following.

(1) Elemental Bi, Te powder with high purity were Chosen as startingmaterial.

(2) The adiabatic temperature can be calculated by using molar enthalpyof forming Bi₂Te₃ and the molar heat capacity according to the followingformula. The molar enthalpy of forming Bi₂Te₃ at 298K Δ_(f)H_(298K) is−78.659 kJ·mol⁻¹−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) Cdt

Assuming the adiabatic temperature is lower than the melting point ofBi₂Te₃, there is no phase transition during the combustion processing.The above formula can be simplified as below.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT

The molar heat capacity of Bi₂Te₃ in solid state is 107.989+55.229×10⁻³TJK⁻¹ mol⁻¹, solve the equation and then the adiabatic temperature can beobtained as 860 K. Since the calculated adiabatic temperature is 860 K,which is lower than the melting point of Bi₂Te₃. The result obtained isconsistent with the assumption. Hence the adiabatic temperature is 860K.

$\begin{matrix}{{\Delta_{f}H_{298\mspace{11mu} K}^{0}} = {{- 78.659}\mspace{14mu}{kJ}\;{mol}^{- 1}}} \\{= {- {\int_{298\mspace{11mu} K}^{T_{ad}}{\left( {107.989 + {55.229 \times 10^{- 3}T}} \right){dT}}}}} \\{= {- \left\lbrack {{107.989 \times \left( {T_{ad} - 298} \right)} + {0.5 \times 55.229 \times 10^{- 3} \times}} \right.}} \\\left. \left( {T_{ad}^{2} - 298^{2}} \right) \right\rbrack\end{matrix}$

(3) Since the molten point of Te and Bi is 722.5 K, 544.44 Krespectively. The component with lower melting point is Bi. The ratiobetween the adiabatic temperature and the melting point of the componentwith lower melting point is 1.58. According to the new criterion forcombustion synthesis, self propogating high temperature reaction betweenBi and Te can be self sustained.

(4) The SHS synthesis of Bi₂Te₃ can be achieved by the following steps.

a) Stoichiometric amounts of high purity Bi(4N), and Te(4N) powders wereweighed and mixed in the agate mortar and then cold-pressed into apellet with the dimension of ϕ15×18 mm under the pressure 8 MPa holdingfor 10 min.

b) The pellet obtained in the step a) was sealed in a silica tube underthe pressure of 10⁻³ Pa and was initiated by point-heating a small part(usually the bottom) of the sample. Once started, a wave of exothermicreactions (combustion wave) passes through the remaining material as theliberated heat of fusion in one section is sufficient to maintain thereaction in the neighboring section of the compact. And then the pelletwas cool down to room temperature in the air.

c) The obtained pellet in the step b) was crushed, hand ground into afine powder, Single phase Bi₂Te₃ compounds is obtained.

Embodiment Example 1.2

Based on the new criterion, the detailed synthesis procedure of Cu₂Se isas following.

(1) Elemental Cu, Se powder with high purity were Chosen as startingmaterial.

(2) The adiabatic temperature can be calculated by using molar enthalpyof forming Cu₂Se and the molar heat capacity according to the followingformula. The molar enthalpy of forming Cu₂Se at 298K Δ_(f)H_(298K) is−66.107 kJmol⁻¹.−Δ_(f) H _(298K) =H _(T) ⁰ =H _(298K) ⁰=∫_(298K) ^(T) ^(ad) CdT

Assuming the adiabatic temperature is lower than the temperature of α-βphase transition of Cu₂Se, there is no phase transition during thecombustion processing. The above formula can be simplified as below.−Δ_(f) H _(298K) =H _(T) ⁰ =H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT

The molar specific heat capacity in solid state of a phase Cu₂Se is58.576+0.077404T Jmol⁻¹ K⁻¹. Substitute the equitation with the heatcapacity and molar enthalpy of forming Cu₂Se. And solve the equation.The calculated adiabatic temperature can be obtained as 922.7 K, whichis much higher than the temperature of α-β phase transition of Cu₂Secorresponding to 395 K. it is inconsistent with the hypothesis.

Assuming the adiabatic temperature is higher than the phase transitiontemperature but is lower than the molten point of Cu₂Se, the formula canbe simplified as below.−Δ_(f) H _(298K) =H _(T) ⁰ =H _(298K) ⁰=∫_(298K) ^(T) ^(tr) C _(p) dT+ΔH_(tr)+∫_(T) _(tr) ^(T) ^(ad) C′ _(p) dT

The molar specific heat capacity in solid state of α phase and β phaseCu₂Se are 58.576+0.077404T Jmol⁻¹K⁻¹, 84.098 Jmol⁻¹K⁻¹, respectively.The molar enthalpy of α-β phase transition of Cu₂Se is 6.820 KJ·mol⁻¹.We substitute the equation with the specific heat capacity and molarenthalpy, and solve the equation. The adiabatic temperature can beobtained as 1001.5 K, which is higher than the α-β phase transitiontemperature and lower than the molten point of Cu₂Se. It is consistentwith the hypothesis. Hence the adiabatic temperature is 1001.5 K.66107=∫₂₉₈ ^(395K)(58.576+0.077404T)dT+6820+∫_(395K) ^(T) ^(ad) 84.098dT

(3) Since the molten point of Cu and Se is 1357 K, 494 K respectively.The component with lower melting point is Se. The ratio between theadiabatic temperature and the melting point of the component with lowermelting point is 2.03. According to the new criterion for combustionsynthesis, self propogating high temperature reaction between Cu and Secan be self sustained.

Embodiment Example 1.3

Based on the new criterion, the detailed synthesis procedure of PbS isas following.

(1) Elemental Pb, S powder with high purity were Chosen as startingmaterial.

(2) The adiabatic temperature can be calculated by using molar enthalpyof forming PbS and the molar heat capacity according to the followingformula. The molar enthalpy of forming PbS at 298K Δ_(f)H_(298K) is−98.324 kJmol⁻¹.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) CdT

Assuming the adiabatic temperature is lower than the molten temperatureof PbS, there is no phase transition during the combustion processing.The above formula can be simplified as below.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT

The molar specific heat capacity of PbS in solid state is46.735+0.009205T Jmol⁻¹K⁻¹. Substitute the equitation with the heatcapacity and molar enthalpy of forming PbS. And solve the equation.98324=∫₂₉₈ ^(T) ^(ad) (46.435+0.009205T)dT

The calculated adiabatic temperature can be obtained as 2023 K, which ismuch higher than the molten point of PbS corresponding to 1392 K. it isinconsistent with the hypothesis.

Assuming the adiabatic temperature is higher than the molten point butis lower than the boiling point of PbS, the formula can be simplified asbelow.−Δ_(f) H _(298K) =H _(298K) ⁰ −H _(T) ⁰=∫_(298K) ^(T) ^(m) C _(p) dT+ΔH_(m)+∫_(T) _(m) ^(t) ^(ad) C″ _(p) dT

The molar specific heat capacity of PbS in solid state is46.735+0.009205T Jmol⁻¹K⁻¹. The molar specific heat capacity of PbS inliquid state is 61.923 Jmol⁻¹K⁻¹. The molar enthalpy between solid stateand liquid state is 36.401 KJmol⁻¹. We substitute the equation with thespecific heat capacity and molar enthalpy, and solve the equation. Theadiabatic temperature can be obtained as 1427 K, which is higher thanthe molten point (1392 K) and lower than the boiling point (1609 K) ofPbS. it is consistent with the hypothesis. Hence the adiabatictemperature is 1427 K.98324=∫_(298K) ^(1392K)(46.435+0.009205T)dT+36401+∫_(1392K) ^(T) ^(ad)61.923dT

(3) Since the molten point of Pb and S is 600 K, 388 K respectively. Thecomponent with lower melting point is S. The ratio between the adiabatictemperature and the melting point of the component with lower meltingpoint is 3.68. According to the new criterion for combustion synthesis,self propogating high temperature reaction between Pb and S can be selfsustained.

By using the method above, the ratio between adiabatic temperature andthe molten point of lower molten point component of Bi₂Se₃, PbSe, Mg₂Snand Mg₂Si are calculated as shown in table 1. The ratio betweenadiabatic temperature and the molten point of lower molten pointcomponent of those compounds thermoelectric is larger than unit. Hence,all those compounds thermoelectric can be synthesized by SHS by choosingsingle elemental as starting materials. However, the adiabatictemperature of all those compounds is dramatically lower than 1800 K. Asan example, the well-known and important thermoelectric compounds Bi₂Te₃and Bi₂Se₃ have their adiabatic temperature well below 1000 K. Accordingto the criterion T_(ad)≥1800 K suggested by Merzhanov, the reactionleading to their formation should not have been self-sustaining.Obviously, the criterion fails in the case of compound semiconductors.

TABLE 1 Parameters of SHS for thermoelectric materials. AdiabaticMaterial Molar enthalpy Specific Heat capacity temperature systemReaction (kJmol⁻¹) (JK⁻¹mol⁻¹) (T_(ad)/K) T_(ad)/T_(m,L) Bi₂Te₃ 2Bi +3Te→Bi₂Te₃ Δ_(f)H⁰ _(298 K): −78.659 107.989 + 55.229 × 10⁻³ T 860 1.58Bi₂Se₃ 2Bi + 3Se→Bi₂Se₃ Δ_(f)H⁰ _(298 K): −139.955 86.818 + 48.953 ×10⁻³ T 995 2.01 ΔmH⁰ _(995 K): 85.772 Cu₂Se 2Cu + Se→Cu₂Se Δ_(f)H⁰_(298 K): −66.107 58.576 + 77.404 × 10⁻³ T 1001 2.03 ΔtH⁰ _(395 K):6.820 84.098 PbS Pb + S→PbS Δ_(f)H⁰ _(298 K): −98.324 46.735 + 9.205 ×10⁻³ T 1427 3.68 ΔmH⁰ _(1392 K): 36.401 61.923 PbSe Pb + Se→PbSe Δ_(f)H⁰_(298 K): −99.998 47.237 + 10.000 × 10⁻³ T 1350 2.73 ΔmH⁰ _(1350 K):49.371 Mg₂Sn 2Mg + Sn→Mg₂Sn Δ_(f)H⁰ _(298 K): −80.000 68.331 + 35.797 ×10⁻³ T + 1.919 × 10⁵ T⁻² 1053 2.01 Mg₂Si 2Mg + Si→Mg₂Si Δ_(f)H⁰_(298 K): −79.496 107.989 + 55.229 × 10⁻³ T 1282 1.39

Based on the success with the combustion synthesis of Cu₂Se, we applythe SHS technique to Bi₂Te₃, Bi₂Se₃, Cu₂Se, PbTe, PbS, PbSe, SnTe, Mg₂Snand Mg₂Si compounds thermoelectric. In each case, high purity powdersare used as a starting material and weighed according to the desiredstoichiometry above. The powders are mixed in an agate mortar and arepressed into pellets. Each respective pellet is sealed in a silica tubeunder the pressure of 10⁻³ Pa. The pellets are locally ignited at thebottom by the flame of a torch.

FIG. 1 shows XRD pattern of the powder after SHS in embodiment example1, which indicate that single phase Bi₂Te₃, Bi₂Se₃, Cu₂Se, PbS, PbSe,Mg₂Sn and Mg₂Si can be obtained after SHS directly. Hence, all compoundswhich can meet the new criterion specifying that the SHS process willproceed whenever the adiabatic temperature exceeds the melting point ofthe lower melting point component of the compact can be synthesized bySHS.

Embodiment Example 2 Embodiment Example 2.1

Based on the new criterion, the detailed synthesis procedure ofMnSi_(1.70) is as following.

(1) Elemental Mn, Si powder with high purity were Chosen as startingmaterial.

(2) The adiabatic temperature can be calculated by using molar enthalpyof forming MnSi_(1.70) and the molar heat capacity according to thefollowing formula. The molar enthalpy of forming MnSi_(1.70) at 298KΔ_(f)H_(298K) is −75.60 kJmol⁻¹.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) CdT

Assuming the adiabatic temperature is lower than the molten point ofMnSi_(1.70) corresponding to 1425 K, there is no phase transition duringthe combustion processing. The above formula can be simplified as below.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT

The molar specific heat capacity of MnSi_(1.70) in solid state is71.927+4.615×10⁻³T−13.067×10⁵T⁻²JK⁻¹ mol⁻¹. Substitute the equitationwith the heat capacity and molar enthalpy of forming MnSi_(1.70). Andsolve the equation. The calculated adiabatic temperature can be obtainedas 1314 K, which is lower than the molten point of MnSi_(1.70)corresponding to 1425 K. it is consistent with the hypothesis. Hence theadiabatic temperature is 1314 K.

$\begin{matrix}{{\Delta_{f}H_{298\mspace{11mu} K}^{0}} = {{- 75.601}\mspace{14mu}{kJmol}^{- 1}}} \\{= {\int_{298\mspace{11mu} K}^{T_{ad}}{\left( {71.927 + {4.615 \times 10^{- 3}T} - {13.067 \times 10^{5}T^{- 2}}} \right){dT}}}} \\{= {- \left\lbrack {{71.927 \times \left( {T_{ad} - 298} \right)} + {0.5 \times 4.615 \times \left( {T_{ad}^{2} - 298^{2}} \right)} +} \right.}} \\\left. {13.067 \times 10^{5}\left( {T_{ad}^{- 1} - {1/298}} \right)} \right\rbrack\end{matrix}$

(3) Since the molten point of Mn and Si is 1519 K, 1687 K respectively.The component with lower melting point is Mn. The ratio between theadiabatic temperature and the molten point of the component with lowermolten point is 0.88. According to the new criterion for combustionsynthesis, self propagating high temperature reaction between Mn and Sito form MnSi_(1.70) cannot be self sustained.

Embodiment Example 2.2

Based on the new criterion, the detailed synthesis procedure of Sb₂Te₃is as following.

(1) Elemental Sb, Te powder with high purity were Chosen as startingmaterial.

(2) The adiabatic temperature can be calculated by using molar enthalpyof forming Sb₂Te₃ and the molar heat capacity according to the followingformula. The molar enthalpy of forming Sb₂Te₃ at 298K Δ_(f)H_(298K) is−56.4841 kJmol⁻¹.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) CdT

Assuming the adiabatic temperature is lower than the molten point ofSb₂Te₃ corresponding to 890.7 K, there is no phase transition during thecombustion processing. The above formula can be simplified as below.−Δ_(f) H _(298K) =H _(T) ⁰ −H _(298K) ⁰=∫_(298K) ^(T) ^(ad) C _(p) dT

The molar specific heat capacity of Sb₂Te₃ in solid state is112.884+53.137×10⁻³T JK⁻¹ mol⁻¹. Substitute the equitation with the heatcapacity and molar enthalpy of forming Sb₂Te₃. And solve the equation.The calculated adiabatic temperature can be obtained as 702 K, which islower than the molten point of Sb₂Te₃ corresponding to 890.7 K. it isconsistent with the hypothesis. Hence the adiabatic temperature is 702K.

$\begin{matrix}{{\Delta_{f}H_{298\mspace{11mu} K}^{0}} = {{- 56.484}\mspace{14mu}{kJmol}^{- 1}}} \\{= {- {\int_{298\mspace{11mu} K}^{T_{ad}}{\left( {112.884 + {53.137 \times 10^{- 3}T}} \right){dT}}}}} \\{= {- \left\lbrack {{112.884 \times \left( {T_{ad} - 298} \right)} + {0.5 \times 53.137 \times 10^{- 3} \times \left( {T_{ad}^{2} - 298^{2}} \right)}} \right\rbrack}}\end{matrix}$

(3) Since the molten point of Sb and Te is 903.755 K, 722.5 Krespectively. The component with lower molten point is Te. The ratiobetween the adiabatic temperature and the molten point of the componentwith lower molten point is 0.98. According to the new criterion forcombustion synthesis, self propagating high temperature reaction betweenSb and Te to form Sb₂Te₃ cannot be self sustained.

Table 2 shows the molar enthalpy of forming Sb₂Te₃ and MnSi_(1.70) at298 K, specific heat capacity of Sb₂Te₃ and MnSi_(1.70), adiabatictemperature T_(ad) and the ratio between the adiabatic temperature andthe molten point of the component with lower molten point. Since thecalculated ratio T_(ad)/T_(m,L) for both materials is less than theunity, i.e., the heat of reaction is too low to melt the lower meltingpoint component. This impedes the reaction speed and prevents thereaction front to self-propagate.

TABLE 2 Thermodynamic parameters for Sb₂Te₃ and MnSi_(1.70). AdiabaticMaterial Molar enthalpy Specific Heat capacity temperature systemReaction (kJmol⁻¹) (JK⁻¹mol⁻¹) (T_(ad)/K) T_(ad)/T_(m,L) Sb₂Te₃ 2Sb +3Te→Sb₂Te₃ Δ_(f)H⁰ _(298 K): −56.484 112.884 + 53.137 × 10⁻³ T 702 0.98MnSi_(1.70) Mn + 1.70Si→MnSi_(1.70) Δ_(f)H⁰ _(298 K): −75.601 71.927 +4.615 × 10⁻³ T − 13.067 × 10⁵ T⁻² 1314 0.88

In order to prove that Sb₂Te₃ cannot be synthesized by SHS, Theexperimental as below has been done. The detailed synthesis procedure isas below.

-   (1) Stoichiometric amounts Sb₂Te₃ of high purity single elemental    Sb, Te powders were weighed and mixed in the agate mortar and then    cold-pressed into a pellet (ϕ15×18 mm) with the pressure of 8 MPa    holding for 10 min.-   (2) The pellet obtained in step (1) was sealed in a silica tube    under the pressure of 10⁻³ Pa and was initiated by point-heating a    small part (usually the bottom) of the sample with hand torch.    Although the reaction between Sb and Te was ignited at the bottom,    the combustion wave cannot be self-propagated and go through the    whole pellet.-   (3) The different parts of the pellet (specifically the bottom and    the top of the pellet) in step (2) were characterized by XRD.

The proof for MnSi_(1.70) that cannot be synthesized by SHS is the sameas that of Sb₂Te₃. The detailed synthesis procedure is as below.

-   (1) Stoichiometric amounts MnSi_(1.70) of high purity single    elemental Mn, Si powders were weighed and mixed in the agate mortar    and then cold-pressed into a pellet.-   (2) The pellet was sealed in a silica tube under the pressure of    10⁻³ Pa and was initiated by point-heating a small part (usually the    bottom) of the sample with hand torch. Although the reaction between    Mn and Si was ignited at the bottom, the combustion wave cannot be    self-propagated and go through the whole pellet.-   (3) The different parts of the pellet (specifically the bottom and    the top of the pellet) in step (2) were characterized by XRD.

FIG. 2 shows the XRD pattern of bottom part of the top part of theMnSi_(1.70) and Sb₂Te₃ pellet. MnSi and Sb₂Te₃ compounds are observedafter ignition by the torch indicating the reaction started. However atthe top the pellets of the mixture none of compounds except singleelemental Mn, Si, Sb, Te, is observed indicating that the reactioncannot be self-sustained after ignition.

Embodiment Example 3

Assessing available experimental data for high temperature ceramics andintermetallics, such as TiB, ZrB₂, TiB₂, TiSi, ZrSi₂, NiAl, CoAl, ZrC,TiC and MoSi₂, which can be synthesized by SHS and meet the criterionsuggested by Merzhanov that the system will not be self-sustainingunless T_(ad) reaches at least 1800 K. the adiabatic temperature and theratio between adiabatic temperature and the molten point of thecomponent with lower molten point are calculated as shown in table 3.The data indicate that the adiabatic temperature of all high temperatureintermetallics (borides, carbides, silicates) is, indeed, more than 1800K. Moreover, the ratio between adiabatic temperature and the moltenpoint of the component with lower molten point of those high temperatureintermetallics (borides, carbides, silicates) is larger than unit, whichcan meet the new criterion.

TABLE 3 Thermodynamic parameter for high temperature ceramics andintermetallics Adiabatic High temperature ceramics temperature andintermetallics Reaction (T_(ad)/K) T_(ad)/T_(mL) TiB Ti + B→TiB 33502.00599 TiB₂ Ti + 2B→TiB₂ 3190 1.91018 ZrB2 Zr + 2B→ZrB₂ 3310 1.78437TiC Ti + C→TiC 3210 1.92216 ZrC Zr + C→ZrC 3400 1.83288 TiSi Ti +Si→TiSi 2000 1.1976 NiAl Ni + Al→NiAl 1910 2.04497 CoAl Co + Al→CoAl1900 2.03426 MoSi2 Mo + 2Si→MoSi₂ 1900 1.12626 ZrSi2 Zr + 2Si→ZrSi₂ 20631.22288

FIG. 3 shows the the ratio between adiabatic temperature and the moltenpoint of the component with lower molten point of the compounds inembodiment example 1 and the high temperature ceramics andintermetallics in embodiment example 3. It is very clear that the ratiobetween adiabatic temperature and the molten point of the component withlower molten point of those high temperature intermetallics (borides,carbides, silicates) is larger than unit, which can meet the newcriterion.

Merzhanov suggested an empirical criterion that the system will not beself-sustaining unless T_(ad) reaches at least 1800 K based on hightemperature ceramics and intermetallics. However, the empiricalcriterion restricted the scope of the material can be synthesized bySHS. In contrast, the adiabatic temperature of thermoelectricsemiconductors is dramatically lower than 1800 K. According to thecriterion T_(ad)≥1800 K, the reaction leading to their formation shouldnot have been self-sustaining. Moreover, at that high temperature above1800 K most thermoelectric compounds would decompose due to highvolatility of their constituent elements. It seems hopeless forthermoelectric materials to be synthesized by SHS. In this disclosure,SHS was applied to synthesize Bi₂Te₃, Bi₂Se₃, Bi₂S₃, Cu₂Se, PbS, PbSe,SnTe, Mg₂Sn and Mg₂Si compounds thermoelectric for the first time.However, we failed to synthesize Sb₂Te₃ and MnSi_(1.70) by SHS. In orderto find the new thermodynamics criterion, we examined the ratio formedby the relevant thermodynamic parameters: the adiabatic temperature,T_(ad), divided by the melting temperature of the lower melting pointcomponent, T_(m,L). For the SHS reaction to be self-sustaining, thevalue of T_(ad)/T_(m,L) should be more than 1.

Embodiment Example 4

The detailed procedure of the ultra-fast preparation method of highperformance Cu₂Se thermoelectric material with nano pores is asfollowing.

-   1) Stoichiometric amounts Cu₂Se of high purity single elemental Cu,    Se powders were weighed and mixed in the agate mortar. And then the    mixed powder was loaded into a stainless steel die and cold-pressed    into a pellet with the size of ϕ12 mm under the pressure of 10 MPa.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by the hot plate with the    temperature of 573 K at the bottom of the sample. Once started, turn    off the hot plate, a wave of exothermic reactions (combustion wave)    passes through the remaining material as the liberated heat of    fusion in one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air. Single phase Cu₂Se with    nanostructures is obtained.-   3) The obtained pellet Cu₂Se in step 2) was crushed, hand ground    into a fine powder, and then the fine powder was loaded into a    graphite die with size of ϕ15 mm and was vacuum sintered by PAS. The    parameter for spark plasma sintering is with the temperature of 973    K with the heating rate 80 K/min and the pressure of 30 MPa holding    for 3 min. The densely bulks Cu₂Se with nanostructure is obtained    after PAS with the size of ϕ15×3 mm. the sample was cut into the    right size for measurement and microstructure characterization by    diamond saw.

FIG. 4 shows the powder XRD pattern of Cu₂Se after SHS and afterSHS-PAS. Single phase Cu₂Se is obtained after SHS and after SHS-PAS.

Table 4 shows the actual composition of the powder in step 2) ofembodiment example 4 and the bulks in step 3 of embodiment example 4characterized by EPMA. The molar ratio between Cu and Se is ranged from2.004:1 to 2.05:1. The actual composition is almost the same as thestoichiometric. This indicates that SHS-PAS technique can control thecomposition very precisely.

FIG. 5 shows the FESEM image of the fracture surface of the sample afterSHS. Nano grains with the size of 20-50 nm distributes homogeneously onthe grains in the micro-scale. FIG. 6 shows the FESEM image of thefracture surface of the sample after SHS-PAS. Lots of Nano pore with thesize of 10-300 nm is observed.

FIG. 7 show the temperature dependence of ZT for Cu₂Se samplesynthesized by SHS-PAS. The maximum ZT about 1.9 is attained at 1000 K,which is much higher than that reported in the reference

TABLE 4 Nominal composition and actual composition for the powder afterSHS and the bulk after SHS-PAS in the embodiment example 4. Actualcomposition Sample Nominal composition characterized by EPMA Powderafter SHS Cu₂Se Cu_(2.004)Se Bulks after SHS-PAS Cu₂Se Cu_(2.05)Se

Embodiment Example 5 a Method for Ultra-Fast Synthesis of HighThermoelectric Performance Half-Heusler Embodiment Example 5.1

The detailed procedure of the ultra-fast preparation method of highperformance ZrNiSn thermoelectric material is as following.

-   1) Stoichiometric amounts ZrNiSn of high purity single elemental    Zr(2.5N), Ni(2.5N), Sn(2.8N) powders were weighed and mixed in the    agate mortar with the weight about 5 gram. And then the mixed powder    was loaded into a stainless steel die and cold-pressed into a pellet    with the size of ϕ12 mm under the pressure of 6 MPa holding for 5    min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by the hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. The whole SHS process takes 2 seconds.-   3) The obtained pellet ZrNiSn in step 2) was crushed, hand ground    into a fine powder, and then the fine powder was loaded into a    graphite die with size of ϕ15 mm and was vacuum sintered by PAS. The    parameter for plasma activated sintering is with the temperature of    1163-1173 K with the heating rate 80-100 K/min and the pressure of    30 MPa holding for 5-7 min. The densely bulks ZrNiSn is obtained    after PAS with the size of ϕ15×3 mm. the sample was cut into the    right size for measurement and microstructure characterization by    diamond saw.

The phase composition of above samples were characterized by XRD. FIG. 8shows XRD pattern for the samples obtained in step 2) and in step 3) ofembodiment example 5.1. Single phase ZrNiSn is obtained in seconds afterSHS. After PAS, XRD pattern does not change. FIG. 9 shows themicrostructure of the sample in step 2) of embodiment example 5.1. FESEMimage shows that the sample is well crystallized with somenanostructures.

Embodiment Example 5.2

The detailed procedure of the ultra-fast preparation method of highperformance Ti_(0.5)Zr_(0.5)NiSn thermoelectric material is asfollowing.

-   1) Stoichiometric amounts Ti_(0.5)Zr_(0.5)NiSn of high purity single    elemental Ti(4N), Zr(2.5N), Ni(2.5N), Sn(2.8N) powders were weighed    and mixed in the agate mortar with the weight about 5 gram. And then    the mixed powder was loaded into a stainless steel die and    cold-pressed into a pellet with the size of ϕ12 mm under the    pressure of 6 MPa holding for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by the hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. The whole SHS process takes 2 seconds.

The phase compositions of above samples were characterized by XRD. FIG.10 shows XRD pattern for the samples obtained in step 2) of embodimentexample 5.2. Single phase Ti_(0.5)Zr_(0.5)NiSn solid solution isobtained in seconds after SHS.

Embodiment Example 5.3

The detailed procedure of the ultra-fast preparation method of highperformance ZrNiSn_(0.98)Sb_(0.02) thermoelectric material is asfollowing.

-   1) Stoichiometric amounts ZrNiSn_(0.98)Sb_(0.02) of high purity    single elemental Zr(2.5N), Ni(2.5N), Sn(2.8N), Sb(5N) powders were    weighed and mixed in the agate mortar with the weight about 5 gram.    And then the mixed powder was loaded into a stainless steel die and    cold-pressed into a pellet with the size of ϕ12 mm under the    pressure of 6 MPa holding for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by the hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. The whole SHS process takes 2 seconds.-   3) The obtained pellet ZrNiSn_(0.98)Sb_(0.02) in step 2) was    crushed, hand ground into a fine powder, and then the fine powder    was loaded into a graphite die with size of ϕ15 mm and was vacuum    sintered by PAS. The parameter for plasma activated sintering is    with the temperature of 1163-1173 K with the heating rate 80-100    K/min and the pressure of 30 MPa holding for 5-7 min. The densely    bulks ZrNiSn_(0.98)Sb_(0.02) is obtained after PAS with the size of    ϕ15×3 mm. The sample was cut into the right size for measurement and    microstructure characterization by diamond saw.

The phase, microstructure and thermoelectric properties of above sampleswere characterized. FIG. 11 shows XRD pattern for the samples obtainedin step 2) and in step 3) of embodiment example 5.3. Single phase ZrNiSnis obtained in seconds after SHS. After PAS, XRD pattern does notchange. FIG. 12 shows the temperature dependence of power factor and ZTfor sample in step 3) of embodiment example 5.3, which is comparablewith the sample synthesized by induction melting with the samecomposition. At 873 K, the maximum ZT is 0.42.

Embodiment Example 6

The detailed procedure of the ultra-fast preparation method of highperformance BiCuSeO thermoelectric material by SHS is as following.

-   1) Stoichiometric amounts BiCuSeO of high purity Bi₂O₃ (4N), Bi    (2.5N), Cu (2.5N), Se (2.8N) powders were weighed and mixed in the    agate mortar with the weight about 10 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ12 mm under the pressure of 6 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by the hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. The whole SHS process takes 2 seconds.

The phase compositions of above samples were characterized by XRD. FIG.13 shows XRD pattern for the samples obtained in step 2) of embodimentexample 6. Almost Single phase BiCuSeO with trace of tiny amountCu_(1.75)Se is obtained after SHS.

Embodiment Example 7 a Method for Ultra-Fast Synthesis of n TypeBi₂Te_(3−x)Se_(x) with High Thermoelectric Performance EmbodimentExample 7.1

The detailed procedure of the ultra-fast preparation method of highperformance n type Bi₂Te_(3−x)Se. thermoelectric material is asfollowing.

-   1) Stoichiometric amounts Bi₂Te_(2.7)Se_(0.3) of high purity single    elemental Bi(4N), Te(4N), Se(4N) powders were weighed and mixed in    the agate mortar with the weight about 25 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ16 mm under the pressure of 10 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hot plate with the    temperature of 773 K at the bottom of the sample. Once started, turn    off the hot plate, a wave of exothermic reactions (combustion wave)    passes through the remaining material as the liberated heat of    fusion in one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air. Single phase    Bi₂Te_(2.7)Se_(0.3) compounds is obtained after SHS.-   3) The obtained pellet Bi₂Te_(2.7)Se_(0.3) in step 2) was crushed,    hand ground into a fine powder, and then the fine powder was loaded    into a graphite die with size of ϕ15 mm and was vacuum sintered by    PAS. The parameter for plasma activated sintering is with the    temperature of 753 K with the heating rate 100 K/min and the    pressure of 20 MPa holding for 5 min. The densely bulks    Bi₂Te_(2.7)Se_(0.3) is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 14 shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 7.1. Single phase Bi₂Te_(2.7)Se_(0.3) isobtained in seconds after SHS. After PAS, XRD pattern does not change.

FIG. 15 shows the FESEM image of the sample in step 3) of embodimentexample 7.1. FESEM image shows typical layer structure is obtained withrandom distributed grains, indicating no preferential orientation.

FIG. 16 shows the temperature dependence of ZT for Bi₂Te_(2.7)Se_(0.3).In comparison with the sample with the composition ofBi_(1.9)Sb_(0.1)Te_(2.55)Se_(0.45) in the reference (Shanyu Wang, J.Phys. D: Appl. Phys, 2010, 43, 335404) synthesized by Melting spinningcombined with Spark plasma sintering. At 426 K, the maximum ZT of samplein step 3 of embodiment 7.1 is 0.95. At the temperature ranged from 300K to 520 K, the average ZT value is larger than 0.7.

Embodiment Example 7.2

The detailed procedure of the ultra-fast preparation method of highperformance n type Bi₂Te_(3−x)Se_(x) thermoelectric material is asfollowing.

-   1) Stoichiometric amounts Bi₂Te_(2.7)Se_(0.3) of high purity single    elemental Bi(4N), Te(4N), Se(4N) powders were weighed and mixed in    the agate mortar with the weight about 25 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ16 mm under the pressure of 10 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by global explosion at 773    K in the furnace for 3 min. And then the pellet was cool down to    room temperature in the air. Single phase Bi₂Te_(2.7)Se_(0.3)    compounds is obtained after SHS.

FIG. 17 shows XRD pattern for the samples obtained in step 2) ofembodiment example 7.2. Single phase Bi₂Te_(2.7)Se_(0.3) is obtained inseconds after global ignition.

Embodiment Example 7.3

The detailed procedure of the ultra-fast preparation method of highperformance n type Bi_(z)Te_(3−x)Se. thermoelectric material is asfollowing.

-   1) Stoichiometric amounts Bi₂Te₂Se of high purity single elemental    Bi(4N), Te(4N), Se(4N) powders were weighed and mixed in the agate    mortar with the weight about 25 gram. And then the mixed powder was    loaded into a stainless steel die and cold-pressed into a pellet    with the size of ϕ16 mm under the pressure of 10 MPa holding for 5    min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hot plate with the    temperature of 773 K at the bottom of the sample. Once started, turn    off the hot plate, a wave of exothermic reactions (combustion wave)    passes through the remaining material as the liberated heat of    fusion in one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air. Single phase Bi_(z)Te₂Se    compounds is obtained after SHS.

FIG. 18 shows the XRD pattern for the samples obtained in step 2) ofembodiment example 7.3. Single phase Bi_(z)Te₂Se is obtained in secondsafter SHS.

Embodiment Example 8 A New Methods for Ultra-Fast Synthesis ofPbS_(1−x)Se_(x) with High Thermoelectric Performance Embodiment Example8.1

The detailed procedure of the ultra-fast preparation method of highperformance n type PbS_(1−x)Se. thermoelectric material is as following.

-   1) Stoichiometric amounts PbS_(0.22)Se_(0.8) of high purity single    elemental Pb(4N), S(4N), Se(4N) powders were weighed and mixed in    the agate mortar with the weight about 4.5 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 5 MPa holding    for 5 min, and then increase the pressure to 8 MPa holding for 10    min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample. Once started, move away the hand torches, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder for XRD characterization.

FIG. 19 shows XRD pattern for the samples obtained in step 3) ofembodiment example 8.1. Single phase PbS_(0.2)Se_(0.8) solid solution isobtained in seconds after SHS.

Embodiment Example 8.2

The detailed procedure of the ultra-fast preparation method of highperformance n type PbS_(1−x)Se_(x) thermoelectric material is asfollowing.

-   1) Stoichiometric amounts PbS_(0.42)Se_(0.6) of high purity single    elemental Pb(4N), S(4N), Se(4N) powders were weighed and mixed in    the agate mortar with the weight about 4.5 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 5 MPa holding    for 5 min, and then increase the pressure to 8 MPa holding for 10    min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder for XRD characterization.

FIG. 20 shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 8.2. Single phase PbS_(0.4)Se_(0.6) isobtained in seconds after SHS. After PAS, XRD pattern does not change.

Embodiment Example 8.3

The detailed procedure of the ultra-fast preparation method of highperformance n type PbS_(1−x)Se_(x) thermoelectric material is asfollowing.

-   1) Stoichiometric amounts PbS_(0.62)Se_(0.4) of high purity single    elemental Pb(4N), S(4N), Se(4N) powders were weighed and mixed in    the agate mortar with the weight about 4.5 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 5 MPa holding    for 5 min, and then increase the pressure to 8 MPa holding for 10    min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder for XRD measurement.

FIG. 21 shows XRD pattern for the samples obtained in step 3) ofembodiment example 8.3. Single phase PbS_(0.6)Se_(0.4) is obtained inseconds after SHS.

Embodiment Example 8.4

The detailed procedure of the ultra-fast preparation method of highperformance n type PbS_(1−x)Se_(x) thermoelectric material is asfollowing.

-   1) Stoichiometric amounts PbS_(0.82)Se_(0.2) of high purity single    elemental Pb(4N), S(4N), Se(4N) powders were weighed and mixed in    the agate mortar with the weight about 4.5 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 5 MPa holding    for 5 min, and then increase the pressure to 8 MPa holding for 10    min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder for XRD measurement.

FIG. 22 shows XRD pattern for the samples obtained in step 3) ofembodiment example 8.4. Single phase PbS_(0.8)Se_(0.2) solid solution isobtained in seconds after SHS.

Embodiment Example 8.5

The detailed procedure of the ultra-fast preparation method of highperformance n type PbS_(1−x)Se. thermoelectric material is as following.

-   1) Stoichiometric amounts PbS_(1.02) of high purity single elemental    Pb(4N), S(4N) powders were weighed and mixed in the agate mortar    with the weight about 4.5 gram. And then the mixed powder was loaded    into a stainless steel die and cold-pressed into a pellet with the    size of ϕ10 mm under the pressure of 5 MPa holding for 5 min, and    then increase the pressure to 8 MPa holding for 10 min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 823 K with the    heating rate 100 K/min and the pressure of 35 MPa holding for 7 min.    The densely bulks PbS is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 23(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 8.5. FIG. 23(b) shows FESEM image of thesample in step 2) of embodiment example 8.5. FIG. 23(c) showstemperature dependence of ZT for the sample synthesized by SHS-PAS andtraditional melting method.

As shown in FIG. 23, Single phase PbS is obtained in seconds after SHS.The grain size distributes in very large scales. After PAS, Single phasePbS can be maintained. In comparison with the sample synthesized bytraditional method, the average ZT above 600 K is much higher for thesample synthesized by SHS-PAS. At 875 K, the maximum ZT is 0.57, whichis one time higher than the sample synthesized by traditional method.

Embodiment Example 9 A New Methods for Ultra-Fast Synthesis of Mg₂Siwith High Thermoelectric Performance Embodiment Example 9.1

The detailed procedure of the ultra-fast preparation method of highperformance n type Mg₂Si based thermoelectric material is as following.

-   1) Stoichiometric amounts Mg_(2.04)Si_(0.996)Sb_(0.004) of high    purity single elemental Mg (4N), Si (4N), Sb (6N) powders were    weighed and mixed in the agate mortar with the weight about 2.1    gram. And then the mixed powder was loaded into a stainless steel    die and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 5 MPa holding for 5 min, and then increase the pressure    to 8 MPa holding for 10 min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 1073 K with    the heating rate 100 K/min and the pressure of 33 MPa holding for 7    min. The densely bulks Mg₂Si_(0.996)Sb_(0.004) is obtained after PAS    with the size of ϕ15×2.5 mm. The sample was cut into the right size    for measurement and microstructure characterization by diamond saw.

FIG. 24(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 9.1. FIG. 24(b) shows FESEM image of thesample in step 2) of embodiment example 9.1. FIG. 24(c) shows FESEMimage of the sample in step 3) of embodiment example 9.1. As shown inFIG. 24, Single phase Mg₂Si is obtained in seconds after SHS. The grainsize distributes in very large scales. After PAS, Single phase Mg₂Si canbe maintained. The relative density of sample is about 98%. Manycleavage planes (the transgranular fracture) can be seen in the crosssection.

Embodiment Example 9.2

The detailed procedure of the ultra-fast preparation method of highperformance n type Mg₂Si based thermoelectric material is as following.

-   1) Stoichiometric amounts Mg_(2.04)Si_(0.99)Sb_(0.01) of high purity    single elemental Mg (4N), Si (4N), Sb (6N) powders were weighed and    mixed in the agate mortar with the weight about 2.1 gram. And then    the mixed powder was loaded into a stainless steel die and    cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 5 MPa holding for 5 min, and then increase the pressure    to 8 MPa holding for 10 min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 1073 K with    the heating rate 100 K/min and the pressure of 33 MPa holding for 7    min. The densely bulks Mg₂Si_(0.99)Sb_(0.01) is obtained after PAS    with the size of ϕ15×2.5 mm. The sample was cut into the right size    for measurement and microstructure characterization by diamond saw.

FIG. 25(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 9.2. FIG. 25(b) shows FESEM image of thesample in step 2) of embodiment example 9.2. FIG. 25(c) shows FESEMimage of the sample in step 3) of embodiment example 9.2. As shown inFIG. 25, Single phase Mg₂Si is obtained in seconds after SHS. The grainsize distributes in very large scales. After PAS, Single phase Mg₂Si canbe maintained. The relative density of sample is about 98%. Manycleavage planes (the transgranular fracture) can be seen in the crosssection.

Embodiment Example 9.3

The detailed procedure of the ultra-fast preparation method of highperformance n type Mg₂Si based thermoelectric material is as following.

-   1) Stoichiometric amounts Mg_(2.04)Si_(0.98)Sb_(0.02) of high purity    single elemental Mg (4N), Si (4N), Sb (6N) powders were weighed and    mixed in the agate mortar with the weight about 2.1 gram. And then    the mixed powder was loaded into a stainless steel die and    cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 5 MPa holding for 5 min, and then increase the pressure    to 8 MPa holding for 10 min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 1073 K with    the heating rate 100 K/min and the pressure of 33 MPa holding for 7    min. The densely bulks Mg₂Si_(0.98)Sb_(0.02) is obtained after PAS    with the size of ϕ15×2.5 mm. The sample was cut into the right size    for measurement and microstructure characterization by diamond saw.

FIG. 26(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 9.3. FIG. 26(b) shows FESEM image of thesample in step 2) of embodiment example 9.3. FIG. 26(c) shows FESEMimage of the sample in step 3) of embodiment example 9.3. As shown inFIG. 26, Single phase Mg₂Si is obtained in seconds after SHS. The grainsize distributes in very large scales. After PAS, Single phase Mg₂Si canbe maintained. The relative density of sample is about 98%. Manycleavage planes (the transgranular fracture) can be seen in the crosssection.

Embodiment Example 9.4

The detailed procedure of the ultra-fast preparation method of highperformance n type Mg₂Si based thermoelectric material is as following.

-   1) Stoichiometric amounts Mg_(2.04)Si_(0.975)Sb_(0.025) of high    purity single elemental Mg (4N), Si (4N), Sb (6N) powders were    weighed and mixed in the agate mortar with the weight about 2.1    gram. And then the mixed powder was loaded into a stainless steel    die and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 5 MPa holding for 5 min, and then increase the pressure    to 8 MPa holding for 10 min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 1073 K with    the heating rate 100 K/min and the pressure of 33 MPa holding for 7    min. The densely bulks Mg₂Si_(0.975)Sb_(0.025) is obtained after PAS    with the size of ϕ15×2.5 mm. The sample was cut into the right size    for measurement and microstructure characterization by diamond saw.

FIG. 27(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 9.4. FIG. 27(b) shows FESEM image of thesample in step 2) of embodiment example 9.4. FIG. 27(c) shows FESEMimage of the sample in step 3) of embodiment example 9.4. As shown inFIG. 27, Single phase Mg₂Si is obtained in seconds after SHS. The grainsize distributes in very large scales. After PAS, Single phase Mg₂Si canbe maintained. The relative density of sample is about 98%. Manycleavage planes (the transgranular fracture) can be seen in the crosssection.

Embodiment Example 9.5

The detailed procedure of the ultra-fast preparation method of highperformance n type Mg₂Si based thermoelectric material is as following.

-   1) Stoichiometric amounts Mg_(2.04)Si_(0.985)Sb_(0.015) of high    purity single elemental Mg (4N), Si (4N), Sb (6N) powders were    weighed and mixed in the agate mortar with the weight about 2.1    gram. And then the mixed powder was loaded into a stainless steel    die and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 5 MPa holding for 5 min, and then increase the pressure    to 8 MPa holding for 10 min.-   2) The pellet obtained in step 1) was initiated by hand torch at the    bottom of the sample in the air. Once started, move away from the    hand torch, a wave of exothermic reactions (combustion wave) passes    through the remaining material as the liberated heat of fusion in    one section is sufficient to maintain the reaction in the    neighboring section of the compact. And then the pellet was cool    down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 1073 K with    the heating rate 100 K/min and the pressure of 33 MPa holding for 7    min. The densely bulks Mg₂Si_(0.985)Sb_(0.015) is obtained after PAS    with the size of ϕ15×2.5 mm. The sample was cut into the right size    for measurement and microstructure characterization by diamond saw.

FIG. 28(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 9.5. FIG. 28(b) shows FESEM image of thesample in step 2) of embodiment example 9.5. FIG. 28(c) shows FESEMimage of the sample in step 3) of embodiment example 9.5. FIG. 28(d)shows temperature dependence of ZT for Mg₂Si_(0.985)Sb_(0.015)synthesized by SHS-PAS and traditional method in the reference (J. Y.Jung, K. H. Park, I. H. Kim, Thermoelectric Properties of Sb-doped Mg₂SiPrepared by Solid-State Synthesis. IOP Conference Series: MaterialsScience and Engineering 18, 142006 (2011).). As shown in FIG. 28, Singlephase Mg₂Si is obtained in seconds after SHS. The grain size distributesin very large scales. After PAS, Single phase Mg₂Si can be maintained.The relative density of sample is about 98%. Many cleavage planes (thetransgranular fracture) can be seen in the cross section. The maximum ZTfor the sample synthesized by SHS-PAS is 0.73, which is the best valuefor Sb doped Mg₂Si.

Embodiment Example 10 a Methods for Ultra-Fast Synthesis ofCu_(a)MSn_(b)Se₄ Powder Embodiment Example 10.1

Here we choose Sb as M, and a is equal to 3. b is equal to 0. TheStoichiometric of the compound is Cu₃SbSe₄.

The detailed procedure of the ultra-fast preparation method of Cu₃SbSe₄thermoelectric material is as following.

-   1) Stoichiometric amounts Cu₃Sb_(1.01)Se₄ of high purity single    elemental Cu (4N), Se (4N), Sb (6N) powders were weighed and mixed    in the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10-15 MPa holding for 5 min.-   3) The pellet obtained in step 2) was initiated by putting the    sealed quartz tube into the furnace for 30 s which was holding at    573 K. And then the pellet was cool down to room temperature in the    air.

FIG. 29 shows XRD pattern for the samples obtained in step 3) ofembodiment example 10.1. Single phase Cu₃SbSe₄ is obtained in 30 secondsafter SHS.

Embodiment Example 10.2

Here we choose Sb as M, and a is equal to 3. b is equal to 0. TheStoichiometric of the compound is Cu₃SbSe₄.

The detailed procedure of the ultra-fast preparation method of Cu₃SbSe₄thermoelectric material is as following.

-   1) Stoichiometric amounts Cu₃Sb_(1.01)Se₄ of high purity single    elemental Cu (4N), Se (4N), Sb (6N) powders were weighed and mixed    in the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10-15 MPa holding for 5 min.-   3) The pellet obtained in step 2) was initiated by putting the    sealed quartz tube into the furnace for 30 s which was holding at    773 K. And then the pellet was cool down to room temperature in the    air.

FIG. 30 shows XRD pattern for the samples obtained in step 3) ofembodiment example 10.2. Single phase Cu₃SbSe₄ is obtained in 30 secondsafter SHS.

Embodiment Example 10.3

Here we choose Zn as M, and a is equal to 2. b is equal to 1. TheStoichiometric of the compound is Cu₂ZnSnSe₄.

The detailed procedure of the ultra-fast preparation method ofCu₂ZnSnSe₄ thermoelectric material is as following.

-   1) Stoichiometric amounts Cu₂ZnSnSe₄ of high purity single elemental    Cu (4N), Se (4N), Zn (4N), Sn (4N) powders were weighed and mixed in    the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10-15 MPa holding for 5 min.-   3) The pellet obtained in step 2) was initiated by putting the    sealed quartz tube into the furnace for 1 min which was holding at    573 K. And then the pellet was cool down to room temperature in the    air.

FIG. 31 shows XRD pattern for the samples obtained in step 3) ofembodiment example 10.3. Single phase Cu₂ZnSnSe₄ is obtained in 60seconds after SHS.

Embodiment Example 10.4

Here we choose Zn as M, and a is equal to 2. b is equal to 1. TheStoichiometric of the compound is Cu₂ZnSnSe₄.

The detailed procedure of the ultra-fast preparation method ofCu₂ZnSnSe₄ thermoelectric material is as following.

-   1) Stoichiometric amounts Cu₂ZnSnSe₄ of high purity single elemental    Cu (4N), Se (4N), Zn (4N), Sn (4N) powders were weighed and mixed in    the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10-15 MPa holding for 5 min.-   3) The pellet obtained in step 2) was initiated by putting the    sealed quartz tube into the furnace for 1 min which was holding at    773 K. And then the pellet was cool down to room temperature in the    air.

FIG. 32 shows XRD pattern for the samples obtained in step 3) ofembodiment example 10.4. Single phase Cu₂ZnSnSe₄ is obtained in 60seconds after SHS.

Embodiment Example 10.5

Here we choose Cd as M, and a is equal to 2. b is equal to 1. TheStoichiometric of the compound is Cu₂CdSnSe₄.

The detailed procedure of the ultra-fast preparation method ofCu₂CdSnSe₄ thermoelectric material is as following.

-   1) Stoichiometric amounts Cu₂ZnSnSe₄ of high purity single elemental    Cu (4N), Se (4N), Cd (4N), Sn (4N) powders were weighed and mixed in    the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10-15 MPa holding for 5 min.-   3) The pellet obtained in step 2) was initiated by putting the    sealed quartz tube into the furnace for 1 min which was holding at    573 K. And then the pellet was cool down to room temperature in the    air.

FIG. 33 shows XRD pattern for the samples obtained in step 3) ofembodiment example 10.5. Single phase Cu₂CdSnSe₄ is obtained in 60seconds after SHS.

Embodiment Example 10.6

Here we choose Sb as M, and a is equal to 3. b is equal to 0. TheStoichiometric of the compound is Cu₃SbSe₄.

The detailed procedure of the ultra-fast preparation method of Cu₃SbSe₄thermoelectric material is as following.

-   1) Stoichiometric amounts Cu₃Sb_(1.02)Se₄ of high purity single    elemental Cu (4N), Se (4N), Sb (6N) powders were weighed and mixed    in the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10-15 MPa holding for 5 min.-   3) The pellet obtained in step 2) was initiated by putting the    sealed quartz tube into the furnace for 30 s which was holding at    573 K. And then the pellet was cool down to room temperature in the    air.

FIG. 34 shows XRD pattern for the samples obtained in step 3) ofembodiment example 10.6. Single phase Cu₃SbSe₄ is obtained in 30 secondsafter SHS.

Embodiment Example 11 a Methods for Ultra-Fast Synthesis of Cu₂SnSe₃Powder Embodiment Example 11.1

The detailed procedure of the ultra-fast preparation method of Cu₂SnSe₃thermoelectric material is as following.

-   1) Stoichiometric amounts Cu_(2.02)SnSe_(3.03) of high purity single    elemental Cu (4N), Se (4N), Sn (4N) powders were weighed and mixed    in the agate mortar with the weight about 5 gram.-   2) And then the mixed powder was loaded into a stainless steel die    and cold-pressed into a pellet with the size of ϕ10 mm under the    pressure of 10 MPa holding for 5 min. and then the pellet was load    into the quartz tube.-   3) The pellet obtained in step 2) was initiated by putting the    sample into the furnace for 30 s which was holding at 573 K. And    then the pellet was cool down to room temperature in the air.

FIG. 35 shows XRD pattern for the samples obtained in step 3) ofembodiment example 11.1. Single phase Cu₂SnSe₃ is obtained in 30 secondsafter SHS.

Embodiment Example 11.2

The detailed procedure of the ultra-fast preparation method of highthermoelectric performance Cu₂SnSe₃ is as following.

-   1) Stoichiometric amounts Cu_(2.02)SnSe_(3.03) of high purity single    elemental Cu (4N), Se (4N), Sn (4N) powders were weighed and mixed    in the agate mortar with the weight about 5 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 10 MPa holding    for 5 min. and then the pellet was load into the quartz tube.-   2) The pellet obtained in step 2) was initiated by putting the    sample into the furnace for 30 s which was holding at 573 K. And    then the pellet was cool down to room temperature in the air.-   3) The obtained pellet in step 2) was crushed, hand ground into a    fine powder, and then the fine powder was loaded into a graphite die    with size of ϕ15 mm and was vacuum sintered by PAS. The parameter    for spark plasma sintering is with the temperature of 803 K with the    heating rate 60 K/min and the pressure of 35 MPa holding for 6 min.    The densely bulks Cu₂SnSe₃ is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 36 shows XRD pattern for the samples obtained in step 2) ofembodiment example 11.2. Single phase Cu₂SnSe₃ is obtained in 30 secondsafter SHS.

FIG. 37 shows XRD pattern for the samples obtained in step 3) ofembodiment example 11.2. Single phase Cu₂SnSe₃ can be maintained afterPAS.

FIG. 38 shows the temperature dependence of ZT for Cu₂SnSe₃. The maximumZT is 0.8.

Embodiment Example 11.3

The detailed procedure of the ultra-fast preparation method of highthermoelectric performance Cu₂SnSe₃ is as following.

-   1) Stoichiometric amounts Cu_(2.02)SnSe_(3.03) of high purity single    elemental Cu (4N), Se (4N), Sn (4N) powders were weighed and mixed    in the agate mortar with the weight about 5 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 10 MPa holding    for 5 min. and then the pellet was load into the quartz tube.-   2) The pellet obtained in step 2) was initiated by putting the    sample into the furnace for 30 s which was holding at 1273 K. Once    the pellet was ignited, move the quartz tube away from the furnace.    The combustion wave was self-propagating through the whole pellet.    And then the pellet was cool down to room temperature in the air.

FIG. 39 shows XRD pattern for the samples obtained in step 2) ofembodiment example 11.3. Single phase Cu₂SnSe₃ is obtained in 30 secondsafter SHS.

Embodiment Example 12 a Methods for Ultra-Fast Synthesis of CoSb₃ BasedThermoelectric Material Embodiment Example 12.1

The detailed procedure of the ultra-fast preparation method of CoSb₃based thermoelectric material is as following.

-   1) Stoichiometric amounts Co_(3.5)Ni_(0.5)Sb₁₂ of high purity single    elemental Co (4N), Ni (4N), Sb (6N) powders were weighed and mixed    in the agate mortar with the weight about 4 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 4 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. Single phase Co_(3.5)Ni_(0.5)Sb₁₂ compounds is obtained    after SHS.-   3) The obtained pellet Co_(3.5)Ni_(0.5)Sb₁₂ in step 2) was crushed,    hand ground into a fine powder, and then the fine powder was loaded    into a graphite die with size of ϕ16 mm and was vacuum sintered by    PAS. The parameter for spark plasma sintering is with the    temperature of 923 K with the heating rate 100 K/min and the    pressure of 40 MPa holding for 8 min. The densely bulks    Co_(3.5)Ni_(0.5)Sb₁₂ is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 40(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 12.1. FIG. 40(b) shows the FESEM image ofthe sample in step 2) of embodiment example 12.1. FIG. 40(c) shows theFESEM image of the sample in step 3) of embodiment example 12.1. Asshown in FIG. 40, Single phase CoSb₃ with trace of tiny amount of Sb isobtained in a very short time after SHS. After PAS, Single phase CoSb₃is obtained. The pore with the size of 20 nm-100 nm is observed betweenthe grain boundaries. The relative density of the sample is no less than98%.

Embodiment Example 12.2

The detailed procedure of the ultra-fast preparation method of CoSb₃based thermoelectric material is as following.

-   1) Stoichiometric amounts Co_(3.8)Fe_(0.2)Sb₁₂ of high purity single    elemental Co (4N), Fe(4N), Sb (6N) powders were weighed and mixed in    the agate mortar with the weight about 4 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 4 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. Single phase Co_(3.8)Fe_(0.2)Sb₁₂ compounds is obtained    after SHS.-   3) The obtained pellet Co_(3.8)Fe_(0.2)Sb₁₂ in step 2) was crushed,    hand ground into a fine powder, and then the fine powder was loaded    into a graphite die with size of ϕ16 mm and was vacuum sintered by    PAS. The parameter for spark plasma sintering is with the    temperature of 923 K with the heating rate 100 K/min and the    pressure of 40 MPa holding for 8 min. The densely bulks    Co_(3.8)Fe_(0.2)Sb₁₂ is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 41(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 12.2. FIG. 41(b) shows the FESEM image ofthe sample in step 2) of embodiment example 12.2. FIG. 41(c) shows theFESEM image of the sample in step 3) of embodiment example 12.2. Asshown in FIG. 41, Single phase CoSb₃ with trace of tiny amount of Sb isobtained in a very short time after SHS. After PAS, Single phase CoSb₃is obtained. The pore with the size of 20 nm-100 nm is observed betweenthe grain boundaries. The relative density of the sample is no less than98%.

Embodiment Example 12.3

The detailed procedure of the ultra-fast preparation method of CoSb₃based thermoelectric material is as following.

-   1) Stoichiometric amounts Co₄Sb_(11.8)Te_(0.2) of high purity single    elemental Co (4N), Te(6N), Sb (6N) powders were weighed and mixed in    the agate mortar with the weight about 4 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 4 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. Single phase Co₄Sb_(11.8)Te_(0.2) compounds is obtained    after SHS.-   3) The obtained pellet Co₄Sb_(11.8)Te_(0.2) in step 2) was crushed,    hand ground into a fine powder, and then the fine powder was loaded    into a graphite die with size of ϕ16 mm and was vacuum sintered by    PAS. The parameter for spark plasma sintering is with the    temperature of 923 K with the heating rate 100 K/min and the    pressure of 40 MPa holding for 8 min. The densely bulks    Co₄Sb_(11.8)Te_(0.2) is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 42(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 12.3. FIG. 42(b) shows the FESEM image ofthe sample in step 2) of embodiment example 12.3. FIG. 42(c) shows theFESEM image of the sample in step 3) of embodiment example 12.3. Asshown in FIG. 42, Single phase CoSb₃ with trace of tiny amount of Sb isobtained in a very short time after SHS. After PAS, Single phase CoSb₃is obtained. The pore with the size of 20 nm-100 nm is observed betweenthe grain boundaries. The relative density of the sample is no less than98%.

Embodiment Example 12.4

The detailed procedure of the ultra-fast preparation method of CoSb₃based thermoelectric material is as following.

-   1) Stoichiometric amounts Co₄Sb_(11.6)Te_(0.4) of high purity single    elemental Co (4N), Te(6N), Sb (6N) powders were weighed and mixed in    the agate mortar with the weight about 4 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 4 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. Single phase Co₄Sb_(11.6)Te_(0.4) compounds is obtained    after SHS.-   3) The obtained pellet Co₄Sb_(11.6)Te_(0.4) in step 2) was crushed,    hand ground into a fine powder, and then the fine powder was loaded    into a graphite die with size of ϕ16 mm and was vacuum sintered by    PAS. The parameter for spark plasma sintering is with the    temperature of 923 K with the heating rate 100 K/min and the    pressure of 40 MPa holding for 8 min. The densely bulks    Co₄Sb_(11.6)Te_(0.4) is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 43(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 12.4. FIG. 43(b) shows the FESEM image ofthe sample in step 2) of embodiment example 12.4. FIG. 43(c) shows theFESEM image of the sample in step 3) of embodiment example 12.4. Asshown in FIG. 43, Single phase CoSb₃ with trace of tiny amount of Sb isobtained in a very short time after SHS. After PAS, Single phase CoSb₃is obtained. The pore with the size of 20 nm-100 nm is observed betweenthe grain boundaries. The relative density of the sample is no less than98%.

Embodiment Example 12.5

The detailed procedure of the ultra-fast preparation method of CoSb₃based thermoelectric material is as following.

-   1) Stoichiometric amounts Co₄Sb_(11.4)Te_(0.6) of high purity single    elemental Co (4N), Te(6N), Sb (6N) powders were weighed and mixed in    the agate mortar with the weight about 4 gram. And then the mixed    powder was loaded into a stainless steel die and cold-pressed into a    pellet with the size of ϕ10 mm under the pressure of 4 MPa holding    for 5 min.-   2) The pellet obtained in step 1) was sealed in a silica tube under    the pressure of 10⁻³ Pa and was initiated by hand torch at the    bottom of the sample. Once started, move away from the hand torch, a    wave of exothermic reactions (combustion wave) passes through the    remaining material as the liberated heat of fusion in one section is    sufficient to maintain the reaction in the neighboring section of    the compact. And then the pellet was cool down to room temperature    in the air. Single phase Co₄Sb_(11.4)Te_(0.6) compounds is obtained    after SHS.-   3) The obtained pellet Co₄Sb_(11.4)Te_(0.6) in step 2) was crushed,    hand ground into a fine powder, and then the fine powder was loaded    into a graphite die with size of ϕ16 mm and was vacuum sintered by    PAS. The parameter for spark plasma sintering is with the    temperature of 923 K with the heating rate 100 K/min and the    pressure of 40 MPa holding for 8 min. The densely bulks    Co₄Sb_(11.4)Te_(0.6) is obtained after PAS with the size of    ϕ15×2.5 mm. The sample was cut into the right size for measurement    and microstructure characterization by diamond saw.

FIG. 44(a) shows XRD pattern for the samples obtained in step 2) and instep 3) of embodiment example 12.5. FIG. 44(b) shows the FESEM image ofthe sample in step 2) of embodiment example 12.5. FIG. 44(c) shows theFESEM image of the sample in step 3) of embodiment example 12.5. Asshown in FIG. 43, Single phase CoSb₃ with trace of tiny amount of Sb isobtained in a very short time after SHS. After PAS, Single phase CoSb₃is obtained. The pore with the size of 20 nm-100 nm is observed betweenthe grain boundaries. The relative density of the sample is no less than98%.

FIG. 45a shows the temperature dependence of ZT for Co_(3.5)Ni_(0.5)Sb₁₂in step 3 of example 12.1 compared with the data from reference (in thereference, the sample synthesized by Melt-annealing and PAS. It takesabout 240 h). The maximum ZT for Co_(3.5)Ni_(0.5)Sb₁₂ synthesized bySHS-PAS is 0.68, which is the best result obtained for this composition.

FIG. 45(b) shows the temperature dependence of ZT forCo₄Sb_(11.4)Te_(0.6) in step 3 of example 12.5 compared with the datafrom reference (In the reference, the sample is synthesized byMelt-annealing and PAS. It takes about 168 h). The maximum ZT forCo_(3.5)Ni_(0.5)Sb₁₂ synthesized by SHS-PAS is 0.98, which is the bestresult obtained for this composition.

We claim:
 1. A method of preparing a thermoelectric material,comprising: 1) weighing powders of reactants including Bi₂O₃, PbO, Bi,Cu, and Se according to a stoichiometric ratio ofBi₂O₃:PbO:Bi:Cu:Se=(1−p):3p:(1−p):3:3, where p=0, 0.02, 0.04, 0.06, 0.08or 0.1, mixing the powders in an agate mortar, and cold-pressing thepowders into a pellet; 2) sealing the pellet in a silica tube under apressure of 10⁻³ Pa, initiating a self-propagating high temperaturesynthesis (SHS) by point-heating a portion of the pellet wherein, oncethe SHS starts, a wave of exothermic reactions passes through theremaining portion of the pellet, cooling down the pellet after reactionin air or quenched in salt water to obtain a cooled-down pelletcontaining Bi_(1−p)Pb_(p)CuSe; and 3) crushing the cooled-down pelletobtained in step 2) into powder, and sintering the powder with plasmaactivated sintering (PAS) to form a bulk material, wherein parameters ofthe PAS include a reaction temperature above 670° C. and a reactionpressure of 30 MPa for 5-7 min, and a final product is a BiCuSeO basedthermoelectric material.